CN109476858B

CN109476858B - Plasticizer blends for chlorine stability of water-soluble films

Info

Publication number: CN109476858B
Application number: CN201780044308.8A
Authority: CN
Inventors: S·尼; 纳塔内尔·R·米兰达
Original assignee: Monosol LLC
Current assignee: Monosol LLC
Priority date: 2016-08-01
Filing date: 2017-08-01
Publication date: 2022-05-13
Anticipated expiration: 2037-08-01
Also published as: BR112019000354A2; MX2019001392A; ES2959269T3; BR112019000354B1; CN109476858A; CA3029969A1; US10202227B2; US20180029763A1; WO2018026749A1; EP3491050A1; JP2019529598A; JP7146734B2; EP3491050B1

Abstract

Disclosed herein are water-soluble films comprising a mixture of a water-soluble polyvinyl alcohol copolymer and a plasticizer blend, the water-soluble polyvinyl alcohol copolymer comprising an anionic monomer having pendant carboxyl groups, and the plasticizer blend comprising a first plasticizer and a second plasticizer, the first plasticizer comprising sorbitol, and the second plasticizer selected from the group consisting of: glycerol, trimethylolpropane, diglycerol, glycerol propylene oxide polymers, glycerol diacetate, 2-methyl-1, 3-propanediol, and combinations thereof, wherein (i) when the total plasticizer in the film is less than 12PHR, then the plasticizer blend comprises sorbitol, glycerol, and at least one additional second plasticizer; (ii) when the total plasticizer in the film is at least 12PHR and less than 20PHR, then the plasticizer blend comprises sorbitol, glycerin, and at least one additional second plasticizer selected from the group consisting of diglycerin, trimethylolpropane, and combinations thereof; and (iii) when the total plasticizer in the film is 20PHR or greater, then sorbitol comprises at least 1/3 of the total plasticizer.

Description

Plasticizer blends for chlorine stability of water-soluble films

Technical Field

The present disclosure relates generally to water-soluble films and related packets. More particularly, the present disclosure relates to polyvinyl alcohol-based water-soluble films that are compatible with caustic chemicals and suitable for vertical form, fill, and seal processing.

Background

Water-soluble polymeric films are commonly used as packaging materials to simplify the dispersion, pouring, dissolution, and dosing of materials to be delivered. The consumer may add the pouched composition directly to a mixing container, such as a bucket, sink, or any container suitable for holding water. Advantageously, this provides accurate dosing while eliminating the need for the consumer to measure the composition. The pouched compositions can also reduce mess associated with dispensing material from the product container, such as pouring or scooping the material. In summary, soluble pre-measured polymeric film pouches provide convenience to consumers for use in a variety of applications.

The water-soluble polymer films used to make currently commercially available bags can be used to contain caustic chemicals. Notably, unit dose pouches containing these chemicals would be particularly advantageous for protecting consumers from direct contact with these chemicals. However, water-soluble polymers and their resulting films may not dissolve completely after prolonged exposure to the caustic chemicals contained therein. These problems can be particularly pronounced when the bag is used, for example, to contain caustic oxidizing compounds such as chlorinated compounds. In addition, as disclosed in U.S. patent No. 7,067,575, certain plasticizers have a significant negative effect on solubility when the film is exposed to an oxidizing agent. However, reducing the amount of plasticizer in the water-soluble film has a detrimental effect on the formability (e.g., vertical form, fill and seal; thermoformability) of the water-soluble film.

Accordingly, there is a need in the art for a water-soluble film that can be formed into a water-soluble package for containing caustic oxidizing chemicals, such as chlorinated compounds, and that remains water-soluble upon storage in contact with such oxidizing chemicals.

Disclosure of Invention

One aspect of the present disclosure provides a plasticized water-soluble film comprising a mixture of: a water-soluble polyvinyl alcohol copolymer comprising an anionic monomer having a pendant carboxyl group, the mixture further comprising a plasticizer blend comprising a first plasticizer comprising sorbitol and a second plasticizer, for example selected from the group consisting of: glycerol, trimethylolpropane, diglycerol, glycerol propylene oxide polymers, glycerol diacetate, 2-methyl-1, 3-propanediol, and combinations thereof, wherein (i) when the total amount of plasticizer included in the film is less than 12PHR, then the plasticizer blend comprises sorbitol, glycerol, and at least one additional second plasticizer; (ii) when the total amount of plasticizer included in the film is at least 12PHR and less than 20PHR, then the plasticizer blend includes sorbitol, glycerin, and at least one additional second plasticizer selected from the group consisting of diglycerin, trimethylolpropane, and combinations thereof; (iii) when the total amount of plasticizer included in the film is 20PHR or more, then sorbitol makes up at least 1/3 (by weight) of the total amount of plasticizer.

Another aspect of the present disclosure provides a sealed article comprising a water-soluble film of the present disclosure, for example, a bag or pouch having the water-soluble film as at least one wall of the bag or pouch.

Another aspect of the present disclosure provides a sealed pouch comprising the water-soluble film of the present disclosure, the pouch encapsulating or otherwise containing an oxidizing composition.

With respect to the compositions herein, it is contemplated that optional features are selected from the various aspects, embodiments, and examples provided herein, including, but not limited to, components and compositional ranges thereof.

Other aspects and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description. While the films, bags, and methods of making the same are susceptible of embodiment in various forms, the following description includes specific embodiments with the understanding that the present disclosure is illustrative and is not intended to limit the invention to the specific embodiments described herein.

Detailed Description

One aspect of the present disclosure provides a water-soluble film comprising a mixture of: a water-soluble polyvinyl alcohol copolymer comprising an anionic monomer having pendant carboxyl groups, the mixture further comprising a plasticizer blend comprising a first plasticizer comprising sorbitol and a second plasticizer selected from the group consisting of: glycerol, trimethylolpropane, diglycerol, glycerol propylene oxide polymers, glycerol diacetate, 2-methyl-1, 3-propanediol, and combinations thereof, wherein (i) when the total amount of plasticizer included in the film is less than 12PHR, then the plasticizer blend comprises sorbitol, glycerol, and at least one additional second plasticizer; (ii) when the total amount of plasticizer included in the film is at least 12PHR and less than 20PHR, then the plasticizer blend includes sorbitol, glycerin, and at least one additional second plasticizer selected from the group consisting of diglycerin, trimethylolpropane, and combinations thereof; (iii) when the total amount of plasticizer included in the film is 20PHR or more, then sorbitol makes up at least 1/3 (by weight) of the total amount of plasticizer.

Optionally, when glycerin is included in the film, it may be included in an amount of at least 2.0 wt.%, based on the total weight of the film. Optionally, the total amount of plasticizer in the film is at least 2PHR, at least 5PHR, or at least 6.5 PHR. Optionally, the total amount of plasticizer is less than about 12PHR, less than about 10PHR, less than about 8PHR, or less than about 7.5PHR, based on the total resins in the film. Optionally, the total amount of plasticizer in the film is in the range of about 15 to about 20PHR, or about 16 to 18PHR, based on the total resins in the film. Also optionally, the total amount of plasticizer in the film is in the range of about 21PHR to about 27PHR, or about 23 to 25PHR, based on the total resins in the film.

In embodiments, the anionic monomeric unit is selected from the group consisting of: vinyl acetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, alkali metal salts of the foregoing, esters of the foregoing, and combinations of the foregoing. Optionally, the anionic monomer units comprise one or more of maleic acid, monoalkyl maleates, dialkyl maleates, monomethyl maleates, dimethyl maleates, maleic anhydride, alkali metal salts of the foregoing, esters of the foregoing, and combinations thereof. Further optionally, the anionic monomeric unit is selected from the group consisting of: maleic acid, monomethyl maleate, dimethyl maleate, maleic anhydride, alkali metal salts of the foregoing, esters of the foregoing, and combinations thereof.

In an embodiment, the PVOH copolymer has a degree of hydrolysis in a range of 87 to 98, or 89 to 97, or 90 to 96. Optionally, the PVOH copolymer has a degree of hydrolysis in a range of 94 to 98. Optionally, the PVOH copolymer has a degree of hydrolysis of about 96.

In embodiments, the water-soluble film of the present disclosure further comprises an antioxidant. Optionally, the antioxidant is selected from the group consisting of: sodium metabisulfite, propyl gallate, citric acid, and combinations thereof. In embodiments, the water-soluble film of the present disclosure further comprises a filler, a surfactant, an anti-blocking agent, or a combination of the foregoing.

In an embodiment, a water-soluble film of the present disclosure having a thickness of about 2 mils (about 0.05mm) dissolves in water at a temperature of 20 ℃ (68 ° f) in 600 seconds or less according to MonoSol test method MSTM-205 after storage in contact with a caustic chemical oxidizer at 23 ℃ and 35% Relative Humidity (RH) for 6 weeks.

In an embodiment, the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 7 to 8PHR, and the plasticizer blend consists essentially of glycerol, sorbitol, and trimethylolpropane.

In an embodiment, the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 24 to 25PHR, and the plasticizer blend consists essentially of a 1:1 wt% mixture of glycerin and sorbitol.

In an embodiment, the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 24 to 25PHR, and the plasticizer blend consists essentially of a 1:1 wt% mixture of trimethylolpropane and sorbitol.

In an embodiment, the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 24 to 25PHR, and the plasticizer blend consists essentially of a 1:1:1 wt% trimethylolpropane, glycerol, and sorbitol mixture.

In an embodiment, the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 16.5 to 17.5PHR, and the plasticizer blend consists essentially of glycerin, sorbitol, and diglycerin.

In an embodiment, the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 16.5 to 17.5PHR, and the plasticizer blend consists essentially of glycerol, sorbitol, and trimethylolpropane.

Another aspect of the present disclosure provides a sealed article comprising the water-soluble film of the present disclosure. Optionally, the article is a vertical form, filled and sealed article.

Another aspect of the present disclosure provides a sealed pouch comprising the water-soluble film of the present disclosure, the pouch encapsulating an oxidizing composition. Optionally, the bag is a vertical form, filled and sealed bag.

In embodiments, the oxidizing composition is a chlorinated or brominated composition. Optionally, the oxidizing agent comprises an oxidizing agent selected from the group consisting of: sodium, calcium and lithium hypochlorite, dichloroisocyanuric acid, trichloroisocyanuric acid, Trichloroisocyanurate (TC), salts and hydrates of the foregoing, 1, 3-dibromo-5, 5-dimethylhydantoin (DBDMH), 2-dibromo-3-nitrilopropionamide (DBNPA), dibromocyanoacetic acid amide, 1-bromo-3-chloro-5, 5-dimethylhydantoin (BCDMH), 2-bromo-2-nitro-1, 3-propanediol, and combinations thereof. Optionally, the oxidizing agent comprises an oxidizing agent selected from the group consisting of: trichloroisocyanurates, 1-bromo-3-chloro-5, 5-dimethylhydantoin, and combinations thereof.

In embodiments, the bag has an internal volume of at least about 25ml, or at least about 100ml, or at least about 150ml, or at least about 200ml, or at least about 250ml, or at least about 300 ml. Optionally, the bag interior volume can be 200L or less, or 100L or less, or 10L or less, or 5L or less. In embodiments, the bag has a length of at least about 12.5cm (about 5 inches), at least about 18cm (about 7 inches), or at least about 23cm (about 9 inches). Optionally, the bag has a length of 10m or less, or 5m or less, or 1m or less.

As used herein, "comprising" means various components, ingredients, or steps that can be used together in the practice of the present disclosure. Thus, the term "comprising" encompasses the more restrictive terms "consisting essentially of and" consisting of. The compositions of the present invention may comprise, consist essentially of, or consist of any of the required and optional elements disclosed herein. For example, a thermoformed packet can "consist essentially of" the film described herein for its thermoformed properties, while including a non-thermoformed film (e.g., the cover), and optional indicia on the film, such as by inkjet printing. The invention illustratively disclosed herein suitably may be practiced in the absence of any element or step which is not specifically disclosed herein.

To be considered a water-soluble film according to the present disclosure, after storage for 6 weeks in contact with a caustic chemical oxidant such as Trichloroisocyanurate (TC) or 1-bromo-3-chloro-5, 5-dimethylhydantoin (BCDMH) at 23 ℃ and 35% Relative Humidity (RH), a film of about 2 mils (about 0.05mm) thickness dissolves in water in 600 seconds or less at a temperature of 20 ℃ (68 ° f) according to MonoSol test method MSTM-205, as described below. Trichloroisocyanurates are generally recognized as strong chlorine-containing oxidants that are useful as disinfectants, algicides, and bactericides, and are widely used in swimming pools and in the domestic sanitation of hydrotherapy. Trichloroisocyanurates release some chlorine as hypochlorous acid upon dissolution, with the balance remaining as "stored chlorine" in the form of chlorinated isocyanurates. When the released hypochlorous acid runs out, the equilibrium shifts and additional hypochlorous acid is released from the "reservoir" until all available chlorine runs out. 1-bromo-3-chloro-5, 5-dimethylhydantoin (BCDMH) is an excellent source of chlorine and bromine because it reacts slowly with water that releases hypochlorous and hypobromous acids. It is used as a chemical disinfectant for the purification of recreational and drinking water.

All percentages, parts and ratios referred to herein are based on the total dry weight of the film composition or the total weight of the inclusion compositions of the present disclosure, as the case may be, and all measurements are made at about 25 ℃, unless otherwise specified. Unless otherwise specified, all such weights as they pertain to listed ingredients are expressed in terms of activity levels, and, therefore, do not include carriers or by-products that may be included in commercially available materials.

All ranges set forth herein include all possible subsets of ranges and any combination of such subset ranges. Unless otherwise stated, default ranges include the stated endpoints. When a range of values is provided, it is understood that each intervening value, to the extent that there is no such stated, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the disclosure, subject to any specifically excluded limit in the stated range. Where stated ranges include one or both of the limits, ranges excluding either or both of those included limits are also contemplated as part of the disclosure.

It is expressly contemplated that for any value described herein, e.g., as part of a range associated with or as a parameter of the described subject matter, a replacement forming part of the description is a functionally equivalent range around the particular value (e.g., "about 40 mm" for the size disclosed as "40 mm").

As used herein, the terms bag and pouch should be considered interchangeable. In certain embodiments, the terms bag and pouch are used to refer to containers made using film and preferably sealed containers having material sealed therein, e.g., in the form of a metered dose delivery system, respectively. The sealed bag may be made by any suitable method, including such processes and features, such as heat sealing, solvent welding, and adhesive sealing (e.g., using a water-soluble adhesive).

As used herein and unless otherwise specified, the terms "wt.%" and "wt%" are intended to refer to the "dry" (non-aqueous) parts of the composition of the identified elements by weight of the entire film, including residual moisture in the film (when applicable) or parts by weight of the entire composition enclosed within a bag (when applicable).

As used herein and unless otherwise specified, the term "PHR" ("PHR") is intended to refer to the composition of the identifying element per one hundred parts of water-soluble polymer (whether PVOH or otherwise) in the water-soluble film.

The film includes a water-soluble polyvinyl alcohol (PVOH) copolymer resin and a plasticizer.

The film may be prepared by any suitable method, including solution casting methods. The film may be used to form containers (bags) by any suitable process including vertical form, fill and seal (VFFS) or thermoforming, as well as solvent sealing or heat sealing of the film layer, for example, around the perimeter of the container. For example, the bag may be used to dose the material to be delivered into a large volume of water.

Unless otherwise specified, films, pouches and related methods of manufacture and use are contemplated to include embodiments that include any combination of one or more of the additional optional elements, features and steps (including those shown in the examples and figures) described further below.

Water-soluble film

The films and related pouches described herein comprise a plasticized water-soluble film. In one aspect, the water-soluble film comprises at least about 50 wt.% total PVOH resin comprising one or more PVOH polymers, optionally including a PVOH copolymer. The film can have any suitable thickness, and the film thickness is typically, and specifically expected to be, about 76 micrometers (μm). Other values and ranges contemplated include values in the range of about 5 to about 200 μm, or in the range of about 20 to about 100 μm, or about 40 to about 90 μm, or about 50 to about 80 μm, or about 60 to about 65 μm, such as 50 μm, 65 μm, 76 μm, or 88 μm.

PVOH resins

The films described herein include one or more polyvinyl alcohol (PVOH) polymers to constitute the PVOH resin content of the film, and can include a PVOH copolymer resin.

Polyvinyl alcohol is a synthetic resin that is typically prepared by alcoholysis, often referred to as hydrolysis or saponification, of polyvinyl acetate. Fully hydrolyzed PVOH, in which almost all of the acetate groups have been converted to alcohol groups, is a strongly hydrogen-bonded, highly crystalline polymer that dissolves only in hot water above about 140 ° f (about 60 ℃). If a sufficient number of acetate groups are allowed to remain after hydrolysis of the polyvinyl acetate, i.e., partially hydrolyzing the PVOH polymer, the polymer is less hydrogen bonded, less crystalline and generally soluble in cold water at less than about 50 ° f (about 10 ℃). Thus, the partially hydrolyzed polymer is a vinyl alcohol-vinyl acetate copolymer, i.e., a PVOH copolymer, but is commonly referred to as PVOH.

In particular, the PVOH resin will include a partially or fully hydrolyzed PVOH copolymer including an anionic monomer unit, a vinyl alcohol monomer unit, and optionally a vinyl acetate monomer unit.

A general class of anionic monomer units useful in PVOH copolymers includes vinyl polymeric units corresponding to monocarboxylic acid vinyl monomers, esters and anhydrides thereof, dicarboxylic acid monomers having polymerizable double bonds, esters and anhydrides thereof, and alkali metal salts of any of the foregoing. In various embodiments, the anionic monomer may be one or more of the following: vinyl acetic acid, alkyl acrylate, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid, monoalkyl citraconate, dialkyl citraconate, citraconic anhydride, mesaconic acid, monoalkyl mesaconate, dialkyl mesaconate, glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate, glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, vinyl sulfonic acid, 2-acrylamido-1-methylpropane sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-methacrylamido-2-methylpropane sulfonic acid, Ethyl 2-sulfoacrylate, alkali metal salts of the foregoing (e.g., sodium, potassium, or other alkali metal salts), esters of the foregoing (e.g., methyl, ethyl, or other C)₁-C₄Or C₆Alkyl esters) and combinations of the foregoing (e.g., multiple anionic monomers or equivalent forms of the same anionic monomer). For example, the anionic monomer may include one or more of monomethyl maleate and alkali metal salts (e.g., sodium salts) thereof. In embodiments, the anionic monomer may be selected from the group consisting of: vinyl acetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconate, itaconic acidDimethyl esters, itaconic anhydride, alkali metal salts of the foregoing, esters of the foregoing, and combinations of the foregoing.

In one type of embodiment, the PVOH is a carboxyl-modified copolymer. In another aspect, the PVOH may be modified with dicarboxylic type monomers. In one class of these embodiments, the alpha carbons of the two carbonyl groups are linked to an unsaturated bond (e.g., maleic acid, fumaric acid). In another class of these embodiments, the alpha carbons of the two carbonyl groups are linked to an unsaturated bond, and the unsaturated bond is further substituted, for example, with a methyl branch (e.g., citraconic acid, mesaconic acid). In another class of these embodiments, the beta carbon of one carbonyl group and the alpha carbon of another carbonyl group are linked to an unsaturated bond (e.g., itaconic acid, cis-glutaconic acid, trans-glutaconic acid). Monomers that provide alkylcarboxy groups are contemplated. Maleic acid type (e.g., maleic acid, dialkyl maleates (including dimethyl maleate), monoalkyl maleates (including monomethyl maleate), or maleic anhydride) comonomers are specifically contemplated. In embodiments, the anionic monomeric unit is selected from the group consisting of: maleic acid, monoalkyl maleates, dialkyl maleates, monomethyl maleates, dimethyl maleates, maleic anhydride, alkali metal salts of the foregoing, esters of the foregoing, and combinations thereof. In embodiments, the anionic monomeric unit is selected from the group consisting of: maleic acid, monomethyl maleate, dimethyl maleate, maleic anhydride, alkali metal salts of the foregoing, esters of the foregoing, and combinations thereof.

When the PVOH resin comprises a PVOH copolymer including an anionic monomer, the level of incorporation of one or more anionic monomer units in the PVOH copolymer is not particularly limited. In embodiments, the one or more anionic monomer units are present in the PVOH copolymer in an amount in a range of about 1 mol.% to 10 mol.%, or 1.5 mol.% to about 8 mol.%, or about 2 mol.% to about 6 mol.%, or about 3 mol.% to about 5 mol.%, or about 1 mol.% to about 4 mol.% (e.g., in various embodiments at least 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, or 4.0 mol.% and/or up to about 3.0, 4.0, 4.5, 5.0, 6.0, 8.0, or 10 mol.%).

PVOH copolymers including anionic monomers are also characterized by the level of pendant anionic groups present in the copolymer. The level of pendant anionic groups in the PVOH copolymer is not particularly limited. In embodiments, the pendant anionic groups are present in the PVOH copolymer in an amount in a range of about 1% to 20%, or 1.5% to 8%, or 2% to 12%, or 2% to 10%, or at least 2.5%, or at least 3%, or at least 3.5%, such as 2%, 3%, 6%, or 8%.

In an embodiment, the amount of PVOH copolymer in the film can be in a range of at least about 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, or 90 wt.%, and/or up to about 60 wt.%, 70 wt.%, 80 wt.%, 90 wt.%, 95 wt.%, or 99 wt.%. If two liquid plasticizers are used, about 75% to about 80% of the PVOH copolymer is specifically contemplated, such as 76%, 77%, or 78%. If two solid plasticizers are used, about 65% to about 75% of the PVOH copolymer is specifically contemplated, such as 67%, 68%, 69%, 70%, 71%, or 72%.

In embodiments, the total PVOH resin content of the film can have a degree of hydrolysis (d.h. or DH) of at least 80%, 84%, or 85% and up to about 99.7%, 98%, 96%, or 80%, for example in a range of about 80% to 99.7%, or 84% to about 90%, or 85% to 88%, or 86.5%, or 88% to 90%, or 94% to 98%, or 85% to 99.7%, or 87% to 98%, or 89% to 97%, or 90% to 96%, for example 90%, 92%, 94%, or 96%. As used herein, the degree of hydrolysis is expressed as the mole percentage of vinyl acetate units converted to vinyl alcohol units.

Without intending to be bound by theory, it is believed that hypochlorite ions generated by the chlorinating agent oxidize pendant hydroxyl (-OH) moieties in the PVOH copolymer film, generating carbonyl groups on the polymer backbone. In addition, hydrochloric acid generated from the chlorinating agent may react with hydroxyl groups to generate unsaturated bonds in the polymer backbone, which leads to discoloration in the film. In either case, removal of the side chain-OH groups renders the membrane increasingly water insoluble.

Thus, without intending to be bound by theory, it is believed that a polyvinyl alcohol resin having a higher degree of hydrolysis (e.g., at least 90%, at least 96%) is advantageous for the water-soluble films of the present disclosure because the presence of a large number of-OH groups allows some of the-OH groups to act as "sacrificial" portions of the chlorinating agent contained in the pouches of the present disclosure, while still maintaining sufficient-OH groups to render the pouches water-soluble.

Viscosity of the oil

The viscosity of the PVOH polymer (μ) was determined by measuring the fresh solution using a Brookfield LV type viscometer with a UL adapter as described in british standard EN ISO 15023-2:2006 annex E Brookfield test method. International practice is to state the viscosity of a 4% aqueous solution of polyvinyl alcohol at 20 ℃. Unless otherwise specified, all viscosities specified herein in centipoise (cP) are understood to refer to the viscosity of a 4% aqueous solution of polyvinyl alcohol at 20 ℃. Similarly, when a resin is described as having (or not having) a particular viscosity, unless otherwise specified, it is desirable to specify that the viscosity is the average viscosity of the resin, which itself has a corresponding molecular weight distribution.

In embodiments, the PVOH resin may have a viscosity average of at least about 10cP, 12cP, 13cP, 13.5cP, 14cP, 15cP, 16cP, or 17cP, and at most about 30cP, 28cP, 27cP, 26cP, 24cP, 22cP, 20cP, 19cP, 18cP, or 17.5cP, for example in a range of about 10cP to about 30cP, or about 13cP to about 27cP, or about 13.5cP to about 20cP, or about 18cP to about 22cP, or about 14cP to about 19cP, or about 16cP to about 18cP, or about 17cP to about 16cP, for example 23cP, or 20cP, or 16.5 cP. Viscosity of PVOH resins and weight average molecular weight of PVOH resins are well known in and of the art

Related, and viscosity is often used to represent

Other water-soluble polymers

Other water-soluble polymers used in addition to PVOH copolymer films can include, but are not limited to: vinyl alcohol-vinyl acetate copolymers, sometimes referred to as PVOH homopolymers; a polyacrylate; a water-soluble acrylate copolymer; polyvinylpyrrolidone; a polyethyleneimine; pullulan; water soluble natural polymers including, but not limited to guar gum, gum arabic, xanthan gum, carrageenan, and starch; water-soluble polymer derivatives including, but not limited to, modified starch, ethoxylated starch, and hydroxypropylated starch; copolymers of the foregoing and combinations of any of the foregoing. Still other water-soluble polymers may include polyalkylene oxides, polyacrylamides, polyacrylic acids and salts thereof, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts thereof, polyaminoacids, polyamides, gelatin, methyl cellulose, carboxymethyl cellulose and salts thereof, dextrin, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, maltodextrin, polymethacrylates, and combinations of any of the foregoing. These water-soluble polymers, whether PVOH or others, are commercially available from a variety of sources.

Plasticizer

Plasticizers are liquids, solids, or semi-solids that are added to a material (typically a resin or elastomer) to make the material softer, more flexible (by lowering the glass transition temperature of the polymer), and easier to handle. The polymer may alternatively be plasticized internally by chemical modification of the polymer or monomer. Additionally or in the alternative, the polymer may be plasticized externally by the addition of a suitable plasticizer. The combination of plasticizers for the films described herein includes sorbitol as a first plasticizer and a second plasticizer selected from the group consisting of: glycerol, diglycerol, Trimethylolpropane (TMP), glycerol propylene oxide polymers (e.g., Voranol)^TM230-. In an embodiment, the plasticizer comprises sorbitol as a first plasticizer, glycerol as a second plasticizer, and an additional second plasticizer selected from the group consisting of: glycerin, trimethylolpropane, and combinations thereof. In one type of embodiment, the water-soluble film is substantially free of plasticizers other than the first and second plasticizers (e.g., completely free of other plasticizers, or other plasticizers less than about 1PHR, or other plasticizers less than about 0.5PHR, or other plasticizers less than about 0.2 PHR). In other embodiments, the water solubilityThe film may include other plasticizers (e.g., sugar alcohols, polyols, or others) in addition to the first and second plasticizers.

Plasticizers may include, but are not limited to, glycerol, diglycerol, sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycols up to 400MW, neopentyl glycol, trimethylolpropane, polyether polyols, sorbitol, 2-methyl-1, 3-propanediol (e.g., MP

) Ethanolamine and mixtures thereof. The plasticizer may be selected from glycerol, sorbitol, diglycerol, trimethylolpropane, glycerol propylene oxide polymers, glycerol diacetate, or combinations thereof. The plasticizer may be selected from the group consisting of glycerin, sorbitol, diglycerin, trimethylolpropane, glycerol propylene oxide polymer, glycerol diacetate, 2-methyl-1, 3-propanediol, or combinations thereof. The plasticizer may be selected from glycerol, sorbitol, diglycerol, trimethylolpropane, or combinations thereof. The plasticizer is a blend comprising at least sorbitol as a first plasticizer. In an embodiment, the plasticizer blend comprises a second plasticizer selected from the group consisting of: glycerin, diglycerin, trimethylolpropane, glycerol propylene oxide polymers, glycerol diacetate, 2-methyl-1, 3-propanediol, and combinations thereof. In an embodiment, the plasticizer blend comprises a second plasticizer selected from the group consisting of: glycerin, diglycerin, trimethylolpropane, and combinations thereof. In one type of embodiment, the plasticizer includes glycerin, sorbitol, and trimethylolpropane. In another type of embodiment, the plasticizer includes glycerin, sorbitol, and diglycerin. In another type of embodiment, the plasticizer includes glycerin, sorbitol, and at least one of trimethylolpropane and diglycerol. In another class of embodiments, the plasticizer blend comprises sorbitol and a glycerin or trimethylolpropane. The total amount of plasticizer may range from about 10 wt.% to about 45 wt.%, or from about 20 wt.% to about 45 wt.%, or from about 15 wt.% to about 35 wt.%, or from about 20 wt.% to about 30 wt.%, for example about 25 wt.%, based on the total film weight. The total amount of plasticizer may also be expressed in parts per 100 parts resin. Thus, the total amount of plasticizer may range from about 2PHR to about 30PHR, about 5PHR to about 25PHR, about 2PHR to about 11PHR, about 5PHR to about 10PHR, about 15PHR to about 20PHR, about 16PHR to about 18PHR, about 21PHR to about 27PHR, about 23PHR to about 25PHR, or less than about 25PHR, less than about 20PHR, less than about 17.5PHR, less than about 12PHR, less than about 10PHR, less than about 8PHR, less than about 7.5PHR, or at least 2PHR, at least 5PHR, at least 6.5PHR, at least 10PHR, or at least 15 PHR. Optionally, glycerol may be used in an amount of at least about 2 wt.% up to about 25 wt.%, or 3 wt.% to about 20 wt.%, or about 4 wt.% to about 14 wt.%, or about 6 wt.% to about 12 wt.%, such as about 9 wt.%, for example about 2PHR to about 15PHR, or about 2PHR to about 10PHR, or about 4PHR to about 7PHR, or about 2PHR to about 5 PHR.

In one aspect of the present disclosure, when the total amount of plasticizer is less than about 12PHR, for example in the range of from about 2PHR to about 11PHR, or from about 5PHR to about 10PHR, or from about 7PHR to about 8PHR, then the plasticizer blend may include sorbitol as a first plasticizer and a second plasticizer comprising: glycerol and at least one diglycerol, trimethylolpropane, glycerol propylene oxide polymer, glycerol diacetate, 2-methyl-1, 3-propanediol, or a combination thereof. Optionally, sorbitol can be used in an amount of from about 1PHR to about 3PHR, or from about 1PHR to about 2 PHR. Optionally, trimethylolpropane, diglycerin, glyceryl propylene oxide polymer, glyceryl diacetate, and 2-methyl-1, 3-propanediol can each be used in amounts of from about 2PHR to about 6PHR, or from about 2PHR to about 3PHR, or from about 3PHR to about 5 PHR. Optionally, glycerol may be used in amounts of from about 1PHR to about 4PHR, or from about 1PHR to about 3PHR, or from about 2PHR to about 3 PHR. In an embodiment, the water-soluble film comprises a PVOH/monomethyl maleate copolymer, the total amount of plasticizer present in the film is in the range of about 7 to about 8PHR, and the plasticizer blend consists essentially of glycerin, sorbitol, and diglycerin. In an embodiment, the water-soluble film comprises a PVOH/monomethyl maleate copolymer, the total amount of plasticizer present in the film is in a range of about 7 to about 8PHR, and the plasticizer blend consists essentially of glycerin, sorbitol, and trimethylolpropane.

On the other hand, when the total amount of plasticizer is in the range of about 12PHR to about 20PHR, for example, about 15PHR to about 20PHR, or about 16PHR to about 18PHR, or about 16.5PHR to about 17.5PHR, then the plasticizer blend may include a combination of sorbitol and glycerin as the first and second plasticizers, and at least one additional second plasticizer selected from trimethylolpropane, diglycerol, and combinations thereof. Optionally, sorbitol may be used in an amount of from about 1PHR to about 6PHR, or from about 3PHR to about 6PHR, or from about 2PHR to about 6PHR, or from about 5PHR to about 6 PHR. Optionally, trimethylolpropane and diglycerol may each be used in an amount of from about 4PHR to about 10PHR, or from about 4PHR to about 6PHR, or from about 5PHR to about 6PHR, or from about 9PHR to about 10 PHR. Optionally, glycerol may be used in amounts of from about 3PHR to about 7PHR, or from about 4PHR to about 6PHR, or from about 5PHR to about 6 PHR. In an embodiment, the water-soluble film comprises a PVOH/monomethyl maleate copolymer, the total amount of plasticizer present in the film is in a range of about 16.5PHR to about 17.5PHR, and the plasticizer blend consists essentially of glycerin, sorbitol, and diglycerin. In an embodiment, the water-soluble film comprises a PVOH/monomethyl maleate copolymer, the total amount of plasticizer present in the film is in a range of about 16.5PHR to about 17.5PHR, and the plasticizer blend consists essentially of glycerin, sorbitol, and trimethylolpropane.

On the other hand, when the total amount of plasticizer is about 20PHR or greater, for example from about 21PHR to about 27PHR, or from about 23PHR to about 25PHR, or from about 24PHR to about 25PHR, then sorbitol constitutes at least 1/3 (by weight) of the total plasticizer contained within the film. In some embodiments, the plasticizer comprises sorbitol as a first plasticizer and glycerin or trimethylolpropane as a second plasticizer. In an alternative embodiment, the plasticizer comprises sorbitol as the first plasticizer and two or more of glycerol, trimethylolpropane, diglycerol, glycerol propylene oxide polymer, glycerol diacetate, and 2-methyl-1, 3-propanediol. Optionally, sorbitol may be used in an amount of from about 6PHR to about 15PHR, or from about 6PHR to about 10PHR, or from about 7PHR to about 9PHR, or from about 10PHR to about 14PHR, or from about 12PHR to about 13 PHR. Optionally, glycerol, trimethylolpropane, diglycerol, glycerol propylene oxide polymer, glycerol diacetate, and 2-methyl-1, 3-propanediol can each be used in amounts of from about 6PHR to about 15PHR, or from about 6PHR to about 10PHR, or from about 7PHR to about 9PHR, or from about 10PHR to about 14PHR, or from about 12PHR to about 13 PHR. In an embodiment, the water-soluble film comprises a PVOH/monomethyl maleate copolymer, the total amount of plasticizer present in the film is in a range of about 24PHR to about 25PHR, and the plasticizer blend consists essentially of a 1:1 wt.% mixture of glycerin and sorbitol. In an embodiment, the water-soluble film comprises a PVOH/monomethyl maleate copolymer, the total amount of plasticizer present in the film is in a range of about 24PHR to about 25PHR, and the plasticizer blend consists essentially of a 1:1 wt.% mixture of trimethylolpropane and sorbitol. In an embodiment, the water-soluble film comprises a PVOH/monomethyl maleate copolymer, the total amount of plasticizer present in the film is in a range of about 24PHR to about 25PHR, and the plasticizer blend consists essentially of a 1:1:1 wt% mixture of trimethylolpropane, glycerol, and sorbitol. .

When an antioxidant is provided in the water-soluble film formulation, the total amount of plasticizer can be at the higher end of the range, for example, greater than about 17.0PHR, greater than about 20PHR, or greater than about 25PHR, or from about 25% to about 400% greater than the amount of plasticizer described above.

Plasticizer levels consistent with the examples described herein are specifically contemplated as representative levels of film formulations having various other ingredients described herein, as well as various upper and lower limits as ranges. In particular embodiments, the specific amount of plasticizer may be selected based on factors described herein, including the desired film flexibility and the conversion characteristics of the water-soluble film. At low plasticizer levels, the film can become brittle, difficult to handle, or prone to cracking. At elevated plasticizer levels, the film may be too soft, too weak, or difficult to handle for the desired use.

Surprisingly and advantageously, the water-soluble films of the present disclosure having higher amounts of plasticizer (e.g., greater than about 12PHR, greater than about 17PHR, or greater than about 20PHR) demonstrate stability to caustic oxidizing chemicals. As used herein, a film having "stability to caustic oxidizing chemicals" refers to a film having a thickness of about 2 mils (about 0.05mm) that dissolves in water in 600 seconds or less at a temperature of 20 ℃ (68 ° f) according to MonoSol test method MSTM-205 after storage for 6 weeks in contact with a caustic chemical oxidizer at 23 ℃ and 35% Relative Humidity (RH). Generally, as the amount of plasticizer increases, the stability of the film to caustic oxidizing chemicals is expected to decrease, because at higher plasticizer levels, the film is generally less crystalline and more flexible, allowing active species, such as protons, to migrate through the film and react more readily with the large number of-OH moieties present on the PVOH resin, rendering the film insoluble. Further surprisingly and advantageously, the water-soluble films of the present disclosure having high amounts of plasticizer, e.g., greater than about 20PHR, and higher amounts of sorbitol, e.g., at least 1/3 (by weight) of the total amount of plasticizer, are particularly stable in the presence of caustic oxidizing chemicals. Without intending to be bound by theory, it is believed that due to the higher molecular weight of sorbitol (relative to, for example, glycerol and trimethylolpropane), at a given PHR/weight, fewer sorbitol plasticizer molecules are present in the membrane, providing a more crystalline and less flexible membrane, and reducing the ability of oxidative active species such as protons to migrate through the membrane.

Antioxidant agent

In an embodiment, the water-soluble film may further comprise an antioxidant, such as a chloride scavenger. For example, suitable antioxidant/chloride scavengers include sulfites, bisulfites, thiosulfates, iodides, nitrites, carbamates, ascorbates, and combinations thereof. In embodiments, the antioxidant is selected from Propyl Gallate (PGA), Citric Acid (CA), Sodium Metabisulfite (SMBS), carbamates, ascorbyl esters, and combinations thereof. In an embodiment, the antioxidant is selected from the group consisting of: sodium metabisulfite, propyl gallate, citric acid, and combinations thereof. The antioxidant may be included in the film in an amount in the range of about 0.25 to about 1.5PHR, for example, about 0.25PHR, about 0.30PHR, about 0.35PHR, about 0.40PHR, about 0.45PHR, about 0.5PHR, about 0.75PHR, about 1.0PHR, about 1.25PHR, or about 1.5 PHR.

Auxiliary film component

The water-soluble film may contain other adjuvants and treatments such as, but not limited to, surfactants, lubricants, mold release agents, fillers, extenders, crosslinking agents, antiblocking agents, antioxidants, detackifiers, antifoams (antifoams), nanoparticles such as layered silicate type nanoclays (e.g., sodium montmorillonite), bleaches (e.g., sodium metabisulfite, sodium bisulfite or others), aversive agents such as bitterants (e.g., denatonium salts such as denatonium benzoate, denatonium sugar and denatonium chloride; sucrose octaacetate; quinine; flavonoids such as quercetin and naringenin; and carotenoids such as picrometharin and strychnine) and pungent agents (e.g., capsaicin, piperine, isothiocyanatoallyl and talloworhizurine), and other functional ingredients in amounts suitable for their intended purposes. In embodiments, the water-soluble film may include fillers, surfactants, anti-blocking agents, or combinations of the foregoing.

Surfactants for water-soluble films are well known in the art. Optionally, a surfactant is included to aid in dispersing the resin solution during casting. Suitable surfactants for use in the water-soluble films of the present disclosure include, but are not limited to, dialkyl sulfosuccinates, fatty acid esters of glycerin and propylene glycol, lactic acid esters of fatty acids, sodium alkyl sulfate, polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80, alkyl polyglycol ethers, lecithin, acetylated fatty acid esters of glycerin and propylene glycol, sodium lauryl sulfate, acetylated esters of fatty acids, myristyl dimethyl amine oxide, trimethyl tallow alkyl ammonium chloride, quaternary ammonium compounds, salts thereof, and combinations of any of the foregoing. Too little surfactant can sometimes produce a film with pores, while too much surfactant can produce a film with a greasy or oily feel from the excess surfactant present on the film surface. Thus, the surfactant may be included in the water-soluble film in an amount of less than about 2phr, such as less than about 1phr, or less than about 0.5 phr.

One type of second component contemplated for use is an anti-foaming agent. The defoaming agent may aid in the coalescence of foam bubbles. Defoamers suitable for use in the water-soluble film according to the present disclosure include, but are not limited to, hydrophobic silicas, such as fineSilicas in particle size or fumed silicas, including Foam available from Emerald Performance Materials

Defoamers, including Foam

327、Foam

UVD、Foam

163、Foam

269、Foam

338、Foam

290、Foam

332、Foam

349、Foam

550 and Foam

339 which is a proprietary non-mineral oil defoamer. In the examples, the defoamer may be used in an amount of 0.5phr or less, e.g., 0.05phr, 0.04phr, 0.03phr, 0.02phr, or 0.01 phr.

Suitable fillers/extenders/antiblocking agents include, but are not limited to, starch, modified starch, crosslinked polyvinylpyrrolidone, crosslinked cellulose, microcrystalline cellulose, silicon dioxide, metal oxides, calcium carbonate, talc, mica, stearic acid and metal salts thereof, such as magnesium stearate. Preferred materials are starch, modified starch and silica. In one type of embodiment, the amount of filler/extender/antiblock agent in the water-soluble film can range from, for example, about 1 wt.% to about 6 wt.%, or about 1 wt.% to about 4 wt.%, or about 2 wt.% to about 4 wt.%, or about 1PHR to about 6PHR, or about 1PHR to about 4PHR, or about 2PHR to about 4 PHR.

The aversion agent may be incorporated into the water-soluble film or may be applied as a coating to the water-soluble film. The aversive agent may be added in an amount to cause an aversive reaction, such as a bitterness value, diluted from its commercial form or otherwise mixed with a solvent to facilitate mixing with other water-soluble film components or application as a coating to the water-soluble film. These solvents may be selected from water, low molecular weight alcohols (methanol, ethanol, etc.) or plasticizers disclosed herein.

Antiblocking agents (e.g. SiO)₂And/or stearic acid) may be present in the film in an amount of at least 0.1PHR, or at least 0.5PHR, or at least 1PHR, or in a range of about 0.1 to 5.0PHR, or about 0.1 to about 3.0PHR, or about 0.4 to 1.0PHR, or about 0.5 to about 0.9PHR, or about 0.5 to about 2PHR, or about 0.5 to about 1.5PHR, or 0.1 to 1.2PHR, or 0.1 to 2.7PHR, such as 0.5PHR, 0.6PHR, 0.7PHR, 0.8PHR, or 0.9 PHR.

Suitable median particle sizes for the antiblock agent include median sizes in the range of from about 3 or about 4 microns to about 11 microns, or from about 4 to about 8 microns, or from about 5 to about 6 microns, for example 5, 6, 7, 8 or 8 microns. Suitable SiO₂Is an untreated synthetic amorphous silica designed for use in aqueous systems.

Chemical stability test

The compatibility of a water-soluble film with a chemical can be determined by evaluating the solubility of the film after exposure to the chemical. The water-soluble film is cast to a desired thickness (about 0.05mm) and pouches containing the chemical composition in contact with the pouch film are formed according to any suitable process, such as vertical form, filling and sealing or thermoforming and sealing, as described above.

Pouches containing chemical compositions in contact with pouch film were stored at ambient conditions (23 ℃ and 35% RH), at 38 ℃ and 10% Relative Humidity (RH), or at 38 ℃ and 80% RH. Conditions may be selected to simulate actual storage conditions for a unit dose bag. Samples were stored for 14 days (2 weeks), 28 days (4 weeks) and 42 days (6 weeks).

After the desired storage time has elapsed, the stability of the film to the chemical composition is determined by measuring the disintegration and dissolution times using MSTM 205, as described below. Higher solubility means better compatibility of the film with the chemical composition stored therein.

Dissolution and disintegration test (MSTM 205)

According to MonoSol test method 205(MSTM 205), a method known in the art, films can be characterized or tested for dissolution and disintegration times. See, for example, U.S. patent No. 7,022,656.

Equipment and materials:

600mL beaker

Electromagnetic stirrer (Labline model No. 1250 or equivalent)

Electromagnetic stirring rod (5cm)

Thermometer (0 to 100 ℃. + -. 1 ℃)

Template, stainless steel (3.8 cm. times.3.2 cm)

Timer (0 to 300 seconds, exact to the nearest second)

Polaroid 35mm slider mount (or equivalent)

MonoSol 35mm slider mount support (or equivalent)

Distilled water

For each membrane to be tested, three test specimens were cut from the membrane sample (i.e., a 3.8cm x 3.2cm specimen) using a stainless steel template. If cut from a film web, the samples should be cut from areas of the web that are evenly spaced along the cross direction of the web. Each test sample was then analyzed using the following procedure.

Each sample was latched in a separate 35mm slide mount.

Fill the beaker with 500mL of distilled water. The water temperature was measured with a thermometer and the water was heated or cooled as necessary to maintain the temperature at 20 ℃ (about 68 ° f).

Mark the height of the water column. An electromagnetic stirrer is placed on the base of the stand. Place the beaker on an electromagnetic stirrer, add an electromagnetic stir bar to the beaker, turn on the stir bar, and adjust the stirring speed until a vortex is created, which is about one fifth the height of the water column. The depth of the eddy current is marked.

Securing the 35mm slider mount in the alligator clip of the 35mm slider mount so that the long end of the slider mount is parallel to the water surface. The depth adjuster of the stand should be set so that when dropped, the end of the clamp will be 0.6cm below the surface of the water. One of the short sides of the slider mount should be against the beaker side while the others are positioned directly above the center of the stirring rod so that the membrane surface is perpendicular to the water flow.

In one action, the fastened slide and clamp are lowered into the water and a timer is started. Disintegration occurs when the film breaks apart. When all visible film was released from the slider mount, the slider was raised out of the water while continuing to monitor the solution for undissolved film fragments. Dissolution occurs when all film fragments are no longer visible and the solution becomes clear.

The results should include the following: complete sample identification; individual and average disintegration and dissolution times; and the water temperature of the sample test.

The film disintegration time (I) and film dissolution time (S) can be corrected to a standard or reference film thickness using the exponential algorithm shown below in equations 1 and 2, respectively.

I_corrected＝I_measuredX (reference thickness/measured thickness)^2.00[1]

S_corrected＝S_measuredX (reference thickness/measured thickness)^2.00[2]

Tensile Strength test and elongation test (ASTM D882)

For tensile strength according to tensile strength test and elongation according to elongation testThe membranes that were characterized or tested were analyzed as follows. The procedure includes determining Tensile strength and determining elongation according to ASTM D882 ("Standard Test Method for Tensile Properties of Thin Plastic sheets") or an equivalent. Use of

A tensile test apparatus (model 5544 tensile tester or equivalent) performs the collection of film data. A minimum of three test specimens are tested in the Machine Direction (MD) (if applicable) per measurement, each test specimen being cut with a reliable cutting tool to ensure dimensional stability and reproducibility. The tests were carried out in a standard laboratory atmosphere at 23. + -. 2.0 ℃ and 35. + -. 5% relative humidity. For tensile strength or elongation measurements, 1 "-wide (2.54cm) samples of single film panels having a thickness of 3.0 ± 0.15 mils (or 76.2 ± 3.8 μm) were prepared. The sample is then transferred to

The tensile tester was run to continue testing while minimizing exposure to a 35% relative humidity environment. A tensile tester equipped with a 500N load cell and calibrated was prepared according to the manufacturer's instructions. With appropriate handle and face (

A handle having a face 2702-. The samples were mounted in a tensile testing machine and analyzed to determine elongation (i.e., with the young's modulus applied) and tensile strength (i.e., the stress required to break the film).

Suitable properties of the films according to the present disclosure are labeled by a tensile strength value (in the Machine Direction (MD)) of at least about 20MPa as measured by the tensile strength test. In various embodiments, the film has a tensile strength value of at least 20MPa and/or at most about 100MPa (e.g., about 20, about 40, about 60, about 80, or about 100 MPa).

Such as by

Suitable properties for the films according to the present disclosure are marked by an elongation value (in the machine direction) of at least about 50%, as measured by a testing machine. In various embodiments, the film has an elongation value of at least 50% and/or at most about 700% (e.g., about 50%, about 100%, about 200%, about 225%, about 250%, about 300%, about 400%, about 425%, about 450%, about 475%, about 500%, about 600%, or about 700%).

Method for producing film

As mentioned above, the present disclosure relates to the manufacture of polyvinyl alcohol films, and in particular to solvent cast films. Processes for solvent casting of PVOH are well known in the art. For example, in a film forming process, a polyvinyl alcohol resin and a second additive are dissolved in a solvent, usually water, metered onto a surface, substantially dried (or force dried) to form a cast film, and the resulting cast film is then removed from the surface of the cast film. The process can be performed batch-wise and more efficiently in a continuous process.

In forming a continuous polyvinyl alcohol film, it is conventional practice to meter the solution onto a moving casting surface, such as a continuously moving metal drum or belt, so that the solvent is substantially removed from the liquid, thereby forming a free-standing cast film, and then peeling the resulting cast film from the casting surface.

Optionally, the water-soluble film may be a free-standing film consisting of a single layer or a plurality of similar layers.

Bag (bag)

The film can be used to create a bag containing the composition to form a pouch. The pouch composition may take any form, such as a powder, gel, paste, liquid, tablet, or any combination thereof. The film may also be used in any other application where improved wet processing and low cold water residue are desired. The film forms at least one side wall of the bag, optionally the entire bag, and preferably an outer surface of the at least one side wall.

The films described herein may also be used to make bags having two or more compartments made from the same film or in combination with films of other polymeric materials. The film may additionally be obtained, for example, by casting, blowing, extruding or blown film extrusion of the same or different polymeric materials, as is known in the art. In one type of embodiment, the polymer, copolymer or derivative thereof suitable for use as the additional membrane is selected from the group consisting of polyvinyl alcohols, polyvinyl pyrrolidones, polyalkylene oxides, polyacrylic acids, celluloses, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamides, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatin, natural gums such as xanthan and carrageenan. For example, the polymer may be selected from the group consisting of polyacrylate and water soluble acrylate copolymers, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, polymethacrylates, and combinations thereof, or from the group consisting of polyvinyl alcohol, polyvinyl alcohol copolymers, and Hydroxypropylmethylcellulose (HPMC), and combinations thereof. One contemplated class of embodiments is characterized by a level of polymer in the packet material, such as the PVOH copolymer described above, which is at least 60% as described above.

The pouch of the present disclosure may comprise at least one sealed compartment. Thus, the bag may comprise a single compartment or multiple compartments. The water-soluble pouch may be formed from two layers of water-soluble polymer film sealed at the interface, or from a single film folded over itself and sealed. One or both of the films includes the PVOH film described above. The film defines an internal pouch container volume containing any desired composition for release into an aqueous environment. The composition is not particularly limited, and includes, for example, any of the various compositions described below. In embodiments comprising multiple compartments, each compartment may contain the same and/or different compositions. In turn, the composition can take any suitable form, including but not limited to liquids, solids, compressed solids (tablets), and combinations thereof (e.g., solids suspended in a liquid). In some embodiments, the pouch comprises first, second, and third compartments, each containing a different first, second, and third composition, respectively.

The compartments of a multi-compartment pouch may have the same or different sizes and/or volumes. The compartments of the multi-compartment pouch of the present invention may be separated or joined in any suitable manner. In an embodiment, the second and/or third and/or subsequent compartment is superimposed on the first compartment. The compartments may be packaged in strings, each compartment being individually separable by a perforation line. Thus, each compartment can be individually torn from the rest of the string by the end user

The bags and/or packs of the present disclosure may comprise one or more different films. For example, in a single compartment embodiment, the bag may be made of one wall folded over on itself and sealed at the edges, or alternatively two walls sealed together at the edges. In a multiple compartment embodiment, the packet may be made of one or more films, such that any given packet compartment may contain walls made of a single film or multiple films having different compositions.

The bag and pouch may be manufactured using any suitable equipment and method. For example, single-compartment bags may be made using vertical form fill, horizontal form fill, or rotary drum fill techniques known in the art. These processes may be continuous or batch. The film may be wetted and/or heated to increase its extensibility. The method may also involve the use of a vacuum to draw the film into a suitable mold. The vacuum that draws the film into the mold may be applied for about 0.2 to about 5 seconds, or about 0.3 to about 3, or about 0.5 to about 1.5 seconds while the film is on the horizontal portion of the surface. For example, this vacuum may be such that it provides a negative pressure in the range of 10 mbar to 1000 mbar, or in the range of 100 mbar to 600 mbar.

The mold in which the bag may be made may be of any shape, length, width and depth depending on the desired size of the bag. The size and shape of the molds may also be different from each other, if desired. For example, the volume of the final bag may be about 5ml to about 300ml, or about 10 to 300ml, or about 20 to about 300ml, and the mold size adjusted accordingly. The pouches and/or packets of the present disclosure can be of any size suitable for providing a unit dose. The size of the unit dose depends on the end use application. For example, a unit dose bag for bulk water applications (e.g., swimming pools) may have an internal volume of greater than 25ml, such as 250 ml. For example, unit dose bags for bulk water applications (e.g., hydrotherapy or hot tubs) may have an internal volume of greater than 25ml, such as 100 ml. In embodiments, the bag may have an internal volume of at least about 25ml, or at least about 100ml, or at least about 150ml, or at least about 200ml, or at least about 250ml, or at least about 300 ml. In embodiments, the contents of the pouch may be a loose powder or a powder in the form of a compressed tablet. The loose powder or compressed tablet may be provided in an amount of at least about 25g, or at least about 100g, or at least about 150g, or at least about 200g, or at least about 250g, or at least about 300g, or at least about 400g, or at least about 500g, or at least about 550g, or at least about 600g, for example in the range of from about 100g to about 600g, or from about 250g to about 550g, or from about 500g to about 600g, or from about 25g to about 300 g. The bags/pouches of the present disclosure may have a length of at least about 12.5cm (about 5 inches), at least about 15.25cm (about 6 inches), at least about 18cm (about 7 inches), or at least about 23cm (about 9 inches). In embodiments, the pouch/bag of the present disclosure may have a width of at least about 7.5cm (about 3 inches), at least about 10cm (about 4 inches), or at least about 12.5cm (about 5 inches). In embodiments, the bag/pouch may have a length of about 12.5cm to about 15.25cm (about 5 to about 6 inches) and a width of about 7.5cm to about 10cm (about 3 to about 4 inches).

In one embodiment, the single compartment or the plurality of sealed compartments contain one composition. The plurality of compartments may each contain the same or different compositions. The composition is selected from a liquid, a solid, or a combination thereof.

Vertical form, fill and seal

In embodiments, the water-soluble film of the present disclosure may form a sealed article. In an embodiment, the sealed article is a vertical form, filled and sealed article. The vertical form, fill and seal (VFFS) process is a conventional automated process. VFFS include a device such as an assembly machine that winds a single sheet of film around a vertically oriented feed tube. The machine heat seals or otherwise secures the opposing edges of the film together to create the side seals and form the hollow tube of film. The machine then heat seals or otherwise creates a bottom seal, defining a container portion with an open top where a top seal will later be formed. The machine introduces a prescribed amount of flowable product into the container portion through the open top end. Once the container contains the desired amount of product, the machine advances the film to another heat sealing device, e.g., to create a top seal. Finally, the machine advances the film to a cutter that cuts the film immediately above the top seal to provide a filled package.

During operation, the assembly machine advances the film from the rollers to form the package. Thus, the film must be able to easily advance through the machine and not adhere to the machine components or be too brittle to break during handling. Surprisingly and advantageously, films of the present disclosure having lower amounts of plasticizer, e.g., less than about 20PHR, less than about 12PHR, or less than about 10PHR, demonstrate good conversion into pouches by VFFS. As noted above, films with low amounts of plasticizer are generally expected to be brittle and not easily converted into bags by VFFS. Thus, films of the present disclosure may be prepared that have one or more advantages, including good stability to caustic oxidizing chemicals and good conversion into bags/bales by VFF.

The water soluble film can be converted by VFFS on a ravema VFFS machine or equivalent. The pouches/bags were prepared in a standard laboratory atmosphere at 78 ° f (about 25.5 ℃) and 24% relative humidity. Unfilled bags and filled bags with salt were produced. The saline bag was filled to 1.2 pounds (about 550g) at the maximum fill level. The horizontal sealing temperature is 225 ° f (about 107 ℃) and the vertical sealing temperature is changed as needed to create a good seal, for example, between about 255 ° f (about 124 ℃) and 280 ° f (about 138 ℃).

Moulding, sealing and thermoforming

A thermoformable film is one that can be shaped by the application of heat and force. Water-soluble films having relatively high levels of plasticizer are believed to be suitable for use in such processes.

Thermoforming a film is a process of heating the film, shaping the film (e.g., in a mold), and then allowing the film to cool, as the film cools the film will retain its shape, such as the shape of the mold. The heat may be applied using any suitable means. For example, the film may be directly heated by: the film is passed under a heating element or through hot air before being fed onto the surface or while the film is on the surface. Alternatively, the film may be heated indirectly, for example by heating a surface or applying a hot object to the film. In an embodiment, the film is heated using infrared light. The membrane may be heated to a temperature in the range of about 50 to about 150 ℃, about 50 to about 120 ℃, about 60 to about 130 ℃, about 70 to about 120 ℃, or about 60 to about 90 ℃. Thermoforming may be performed by one or more of the following processes: the heat softened film is manually masked on the mold, or compression molded to the mold (e.g., vacuum formed), or a fresh extrusion plate with an accurately known temperature is automatically indexed into the forming and trimming station at high speed, or the film is automatically placed, plugged, and/or pneumatically stretched and pressed.

Alternatively, the film may be wetted by any suitable means, such as direct wetting by spraying a wetting agent (including a solution of water, the film composition, a plasticizer for the film composition, or any combination of the foregoing) onto the film prior to feeding the film onto the surface or while on the surface; indirect wetting is performed either by wetting the surface or by applying a wet article to the membrane.

After the film has been heated and/or wetted, it may be drawn into a suitable mold, preferably using a vacuum. Filling of the molded membrane may be accomplished by using any suitable means. In embodiments, the most preferred method will depend on the product form and the desired filling speed. In an embodiment, the molded film is filled by an in-line filling technique. The filled open-ended bag is then closed by any suitable method using a second film to form a pouch. This can be done in a horizontal position and using a continuous constant motion approach. The closure can be accomplished by: a second film, preferably a water-soluble film, is continuously fed over and onto the open-topped bag and then the first and second films are preferably sealed together, typically in the region between the dies and thus between the bags.

Any suitable method of sealing the packet and/or its individual compartments may be employed. Non-limiting examples of such means include heat sealing, solvent welding, solvent or wet sealing, and combinations thereof. Typically, only the area where the seal is formed is treated with heat or solvent. The heat or solvent may be applied by any method, typically to the closure material, and typically only to the area intended to form the seal. If a solvent or wet seal or weld is used, it is preferred that heat is also applied. Preferred wet or solvent sealing/welding methods include the selective application of solvent to the areas between the molds or to the closure material by, for example, spraying or printing the solvent onto these areas and then applying pressure on these areas to form the seal. For example, sealing rolls and belts as described above may be used (optionally also providing heat).

The formed bag may then be cut by a cutting device. The cutting may be accomplished using any known method. It is preferred that the cutting can also be performed in a continuous manner, and preferably at a constant speed and preferably while in a horizontal position. The cutting means may for example be a sharp object, or a hot object, or a laser, whereby in the latter case the hot object or laser 'burns' through the film/sealing area.

The different compartments of a multi-compartment pouch may be used together in a side-by-side fashion, with or without cutting the resulting interconnected pouch apart. Alternatively, the compartments may be manufactured separately.

In an embodiment, the pouch may be prepared according to a process comprising the steps of: a) forming a first compartment (as described above); b) forming a recess in some or all of the closed compartments formed in step (a) to produce a second molded compartment that is stacked over the first compartment; c) filling and closing the second compartment by means of a third layer of film; d) sealing the first, second and third films; and e) cutting the film to produce a multi-compartment pouch. The grooves formed in step (b) may be achieved by applying a vacuum to the compartments prepared in step (a).

In an embodiment, the second and/or third compartment may be prepared in a separate step and then combined with the first compartment, as described in european patent application No. 08101442.5 or U.S. patent application publication No. 2013/240388a1 or WO 2009/152031.

In an embodiment, the pouch may be prepared according to a process comprising the steps of: a) forming a first compartment using a first film on a first former, optionally using heat and/or vacuum; b) filling the first compartment with a first composition; c) deforming the second film, optionally using heat and vacuum, on a second forming machine to produce a second and optionally a third molded compartment; d) filling the second compartment and optionally the third compartment; e) sealing the second compartment and optionally the third compartment with a third film; f) placing the sealed second compartment and optionally the third compartment on the first compartment; g) sealing the first, second and optionally third compartments; and h) cutting the film to produce a multi-compartment pouch.

The first and second molding machines may be selected based on their suitability to perform the processes described above. In an embodiment, the first forming machine is preferably a horizontal forming machine and the second forming machine is preferably a rotating drum forming machine, which is preferably positioned above the first forming machine.

It will be appreciated that by using appropriate feed stations, it is possible to manufacture multi-compartment bags incorporating a plurality of different or unique compositions and/or different or unique liquid, gel or paste compositions.

In embodiments, the film and/or bag is sprayed or sprinkled with a suitable material, such as an active agent, a lubricant, an aversive agent, or mixtures thereof. In embodiments, the film and/or pouch is printed, for example, using ink and/or active agent.

Bag contents

The articles of the invention (e.g., in the form of bags or pouches) can contain various compositions, such as water treatment compositions. The multi-compartment pouch may contain the same or different compositions in each individual compartment. The composition approaches a water-soluble film. The composition may be less than about 10cm, or less than about 5cm, or less than about 1cm from the film. Typically, the composition is adjacent to or in contact with the membrane. The film may be in the form of a pouch or compartment in which the composition is contained.

In the examples, a water-soluble film is formed into a sealed pouch, for example by VFFS, and the oxidizing composition is encapsulated. In embodiments, the oxidizing composition is a chlorinated or brominated composition. In an embodiment, the oxidizing composition is a water treatment agent. Such agents include aggressive oxidizing chemicals, for example as described in U.S. patent application publication No. 2014/0110301 and U.S. patent No. 8,728,593. For example, the disinfecting agent may include hypochlorites such as sodium hypochlorite, calcium hypochlorite, and lithium hypochlorite; chlorinated isocyanurates, such as dichloroisocyanuric acid (also known as "dichloro" or dichloro-s-triazinetrione, 1, 3-dichloro-1, 3, 5-triazinane-2, 4, 6-trione) and trichloroisocyanuric acid (also known as "trichloro" or 1,3, 5-trichloro-1, 3, 5-triazinane-2, 4, 6-trione) or Trichloroisocyanurate (TC); chlorates and perchlorates. Salts and hydrates of the disinfecting compounds are also contemplated. For example, dichloroisocyanuric acid may be provided in the form of sodium dichloroisocyanurate, sodium dichloroisocyanurate dihydrate, or the like. Bromine-containing disinfectants are also suitable for use in unit dose package applications, such as brominated isocyanurates, bromates, perbromates, 1, 3-dibromo-5, 5-dimethylhydantoin (DBDMH), 2-dibromo-3-nitrilopropionamide (DBNPA), dibromocyanoacetic acid amide, 1-bromo-3-chloro-5, 5-dimethylhydantoin (BCDMH); and 2-bromo-2-nitro-1, 3-propanediol, and the like. Other suitable oxidizing agents include, but are not limited to, perborates, periodates, persulfates, permanganates, chromates, dichromates, nitrates, nitrites, peroxides, ketone peroxides, peroxyacid mineral acids, and combinations thereof. In an embodiment, the oxidizing agent comprises an oxidizing agent selected from the group consisting of: sodium, calcium and lithium hypochlorite, dichloroisocyanuric acid, trichloroisocyanuric acid, Trichloroisocyanurate (TC), salts and hydrates of the foregoing, 1, 3-dibromo-5, 5-dimethylhydantoin (DBDMH), 2-dibromo-3-nitrilopropionamide (DBNPA), dibromocyanoacetic acid amide, 1-bromo-3-chloro-5, 5-dimethylhydantoin (BCDMH), 2-bromo-2-nitro-1, 3-propanediol, and combinations thereof. In an embodiment, the oxidizing agent comprises an oxidizing agent selected from the group consisting of: trichloroisocyanurates, 1-bromo-3-chloro-5, 5-dimethylhydantoin, and combinations thereof.

Specifically contemplated embodiments of the present disclosure are described herein in the following numbered paragraphs. These examples are intended to be illustrative and are not intended to be limiting.

1. A water-soluble film comprising a mixture of a water-soluble polyvinyl alcohol copolymer and a plasticizer blend, the copolymer comprising an anionic monomer having pendant carboxyl groups, and the plasticizer blend comprising a first plasticizer and a second plasticizer, the first plasticizer comprising sorbitol, and the second plasticizer selected from the group consisting of: glycerol, trimethylolpropane, diglycerol, glycerol propylene oxide polymer, glycerol diacetate, 2-methyl-1, 3-propanediol, and combinations thereof, wherein

(i) When the total amount of plasticizer included in the film is less than 12PHR, then the plasticizer blend comprises sorbitol, glycerin, and at least one additional second plasticizer;

(ii) when the total amount of plasticizer included in the film is at least 12PHR and less than 20PHR, then the plasticizer blend comprises sorbitol, glycerin, and at least one additional second plasticizer selected from the group consisting of diglycerin, trimethylolpropane, and combinations thereof; and

(iii) when the total amount of plasticizer included in the film is 20PHR or more, then sorbitol constitutes at least 1/3 (by weight) of the total amount of plasticizer.

2. The water-soluble film of paragraph 1, wherein when glycerin is included in the film, the glycerin is included in an amount of at least 2.0 wt.%, based on the total weight of the film.

3. The water-soluble film of paragraph 1 or paragraph 2, wherein the total amount of plasticizer in the film is at least 2PHR, at least 5PHR, or at least 6.5PHR, based on the total resin in the film.

4. The water-soluble film of any of paragraphs 1 to 3, wherein the total amount of plasticizer is less than about 12PHR, less than about 10PHR, less than about 8PHR, or less than about 7.5PHR, based on the total resin in the film.

5. The water-soluble film of paragraph 1 or paragraph 2, wherein the total amount of plasticizer in the film is in the range of about 15 to about 20PHR, or about 16 to 18PHR, based on the total resin in the film.

6. The water-soluble film of paragraph 1 or paragraph 2, wherein the total amount of plasticizer in the film is in the range of about 21PHR to about 27PHR, or about 23 to 25PHR, based on the total resin in the film.

7. The water-soluble film of any of the preceding paragraphs, wherein the anionic monomeric units are selected from the group consisting of: vinyl acetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, alkali metal salts of the foregoing, esters of the foregoing, and combinations of the foregoing.

8. The water-soluble film of paragraph 7, wherein the anionic monomer units comprise one or more of maleic acid, monoalkyl maleates, dialkyl maleates, monomethyl maleates, dimethyl maleates, maleic anhydride, alkali metal salts of the foregoing, esters of the foregoing, and combinations thereof.

9. The water-soluble film of paragraph 8, wherein the anionic monomeric unit is selected from the group consisting of: maleic acid, monomethyl maleate, dimethyl maleate, maleic anhydride, alkali metal salts of the foregoing, esters of the foregoing, and combinations thereof.

10. The water-soluble film of any of the preceding paragraphs, wherein the PVOH copolymer comprises a degree of hydrolysis in a range of 87 to 98, or 89 to 97, or 90 to 96.

11. The water-soluble film of paragraph 10, wherein the PVOH copolymer has a degree of hydrolysis in a range of 94 to 98.

12. The water-soluble film of paragraph 11, wherein the PVOH copolymer has a degree of hydrolysis of 96.

13. The water-soluble film of any of the preceding paragraphs, further comprising an antioxidant.

14. The water-soluble film of paragraph 13, wherein the antioxidant is selected from the group consisting of: sodium metabisulfite, propyl gallate, citric acid, and combinations thereof.

15. The water-soluble film of any of the preceding paragraphs, wherein after storage in contact with a caustic chemical oxidant at 23 ℃ and 35% Relative Humidity (RH) for 6 weeks, a film having the same composition and about 2 mils (about 0.05mm) thickness dissolves in water at a temperature of 20 ℃ (68 ° f) in 600 seconds or less according to MonoSol test method MSTM-205.

16. The water-soluble film of any of the preceding paragraphs, further comprising a filler, a surfactant, an anti-blocking agent, or a combination of the foregoing.

17. The water-soluble film of paragraph 1, wherein the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 7 to 8PHR, and the plasticizer blend consists essentially of glycerin, sorbitol, and diglycerin.

18. The water-soluble film of paragraph 1, wherein the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 7 to 8PHR, and the plasticizer blend consists essentially of glycerin, sorbitol, and trimethylolpropane.

19. The water-soluble film of paragraph 1, wherein the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 24 to 25PHR, and the plasticizer blend consists essentially of a 1:1 wt% mixture of glycerin and sorbitol.

20. The water-soluble film of paragraph 1, wherein the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 24 to 25PHR, and the plasticizer blend consists essentially of a 1:1 wt% mixture of trimethylolpropane and sorbitol.

21. The water-soluble film of paragraph 1, wherein the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 24 to 25PHR, and the plasticizer blend consists essentially of a 1:1:1 wt% mixture of trimethylolpropane, glycerol, and sorbitol.

22. The water-soluble film of paragraph 1, wherein the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 16.5 to 17.5PHR, and the plasticizer blend consists essentially of glycerin, sorbitol, and diglycerol.

23. The water-soluble film of paragraph 1, wherein the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 16.5 to 17.5PHR, and the plasticizer blend consists essentially of glycerol, sorbitol, and trimethylolpropane.

24. A sealed article comprising the water-soluble film of any of the preceding paragraphs.

25. The sealed article of paragraph 24, wherein the article is a vertical form, filled and sealed article.

26. A sealed pouch comprising the film of any of the preceding paragraphs, the pouch encapsulating an oxidizing composition.

27. The sealed bag of paragraph 26, wherein the bag is a vertical form, fill, and seal bag.

28. The sealed pouch of paragraph 26 or paragraph 27, wherein the oxidizing composition is a chlorinated or brominated composition.

29. The sealed pouch of any of paragraphs 26 to 28, wherein the oxidizing agent comprises an oxidizing agent selected from the group consisting of: sodium, calcium and lithium hypochlorite, dichloroisocyanuric acid, trichloroisocyanuric acid, Trichloroisocyanurate (TC), salts and hydrates of the foregoing, 1, 3-dibromo-5, 5-dimethylhydantoin (DBDMH), 2-dibromo-3-nitrilopropionamide (DBNPA), dibromocyanoacetic acid amide, 1-bromo-3-chloro-5, 5-dimethylhydantoin (BCDMH), 2-bromo-2-nitro-1, 3-propanediol, and combinations thereof.

30. The sealed pouch of any of paragraphs 26 to 29, wherein the oxidizing agent comprises an oxidizing agent selected from the group consisting of: trichloroisocyanurates, 1-bromo-3-chloro-5, 5-dimethylhydantoin, and combinations thereof.

31. The sealed bag of any of paragraphs 27 to 30, wherein the bag has an internal volume of at least about 25ml, or at least about 100ml, or at least about 150ml, or at least about 200ml, or at least about 250ml, or at least about 300 ml.

32. The sealed bag of any of paragraphs 27 to 31, wherein the bag has a length of at least about 12.5cm (about 5 inches), at least about 18cm (about 7 inches), or at least about 23cm (about 9 inches).

The water-soluble films according to the present disclosure may be better understood from the following examples, which are intended only to illustrate water-soluble films and are not intended to limit the scope thereof in any way.

Examples of the invention

Example 1: compatibility of films with Trichloroisocyanurates (TC)

Trichloroisocyanurates are among the strongest chlorine-containing oxidants for swimming pool and spa water treatment. Water-soluble films comprising PVOH/monomethyl maleate or PVOH/2-acrylamide-2-methylpropanesulfonic Acid (AMPS) copolymers were prepared having the plasticizers described in tables 1 and 2 below. The thickness of the film was 1.5 mils (about 38 μm). The pouches were prepared by encapsulating about 16mg of trichloroisocyanurate in the film. The solubility of the water soluble film of the water soluble pouch was tested at t ═ 0 (no storage), 2 weeks, 4 weeks, and 6 weeks. The bags were stored at 23 ℃ and 35% RH. The dissolution time of each bag was determined at 21 ℃ according to MSTM 205. The films dissolved within 600 seconds after 6 weeks of storage are indicated as (+). The film that did not dissolve within 600 seconds after 6 weeks of storage is designated (-) in tables 1 and 2.

TABLE 1

¹MMM-1 is a PVOH/monomethyl maleate copolymer having a 4.0 mol% maleate modification and a 96 mol% degree of hydrolysis.

²AMPS is a PVOH/2-acrylamido-2-methylpropane sulfonic acid copolymer modified with 4.0 mol% AMPS.

³MMM-2 is a PVOH/monomethyl maleate copolymer having a 4.0 mol% maleate modification and a 90 mol% degree of hydrolysis.

Table 1 shows that films of the present disclosure comprising PVOH copolymers comprising anionic monomers having pendant carboxyl groups, and having a first plasticizer comprising sorbitol and a second plasticizer comprising glycerol and at least one trimethylolpropane or diglycerol, are compatible with trichloroisocyanurates when the total amount of plasticizer is in the range of 12PHR to 20 PHR. This is achieved byIn addition, films of the present disclosure comprising PVOH copolymers comprising anionic monomers having pendant carboxyl groups and having a first plasticizer comprising sorbitol and at least one 2-methyl-1, 3-propanediol, trimethylolpropane, glycerol propylene oxide polymer (e.g., Voranol) are compatible with trichloroisocyanurates when the total amount of plasticizer is less than 12phr^TM230-660), diacetin, and diglycerin. Conversely, when the additional plasticizer is trimethylolpropane or glycerol diacetate, the film comprising a PVOH copolymer comprising an anionic monomer that does not include pendant carboxyl groups is compatible with trichloroisocyanurates, but the film comprises less than 12phr of the total amount of plasticizer, a first plasticizer comprising sorbitol, and at least one polymer selected from 2-methyl-1, 3-propanediol, trimethylolpropane, glycerol propylene oxide (e.g., Voranol^TM230-660), diacetin and diglycerin.

TABLE 2

Table 2 shows that when the total amount of plasticizer is less than 20PHR, for example, in the range of about 12PHR to about 20PHR (e.g., samples 7, 10, 12, and 15), films comprising PVOH copolymers having anionic monomers with pendant carboxyl groups further comprising a first plasticizer comprising sorbitol and a second plasticizer comprising glycerol and at least one of diglycerol or trimethylolpropane are compatible with trichloroisocyanurates. Table 2 also shows that when sorbitol comprises at least 1/3 of the total amount of plasticizer (e.g., samples 32-35), the film comprising the PVOH copolymer having an anionic monomer with pendant carboxyl groups is compatible with trichloroisocyanurates, the film further comprising a first plasticizer comprising sorbitol and a total plasticizer amount greater than 20 PHR.

Example 2: films with trichloroisocyanides in the presence of an antioxidantUreaCompatibility of acid esters (TC)

A water-soluble film comprising a PVOH/monomethyl maleate copolymer was prepared and converted to a bag containing trichloroisocyanurate having the plasticizers shown in table 3 as described in example 1. Film samples 36-41 also included antioxidants in the amounts listed in table 3 below and were compared to film samples 2, 7, and 12 prepared in example 1 without any antioxidants. Solubility data for the water-soluble film of the water-soluble pouch was obtained as described in example 1.

TABLE 3

⁴PGA is propyl gallate

⁵CA is citric acid.

⁶SMBS is sodium metabisulfite.

Table 3 shows that films comprising PVOH copolymers having anionic monomers including pendant carboxyl groups, the films further comprising a first plasticizer comprising sorbitol and a second plasticizer comprising glycerol and trimethylolpropane, wherein the total amount of plasticizer is greater than 20PHR and the amount of sorbitol is less than 1/3 of the total amount of plasticizer (e.g., film sample 2), can be made compatible with trichloroisocyanurates when the antioxidant is included in the film in an amount in the range of about 0.25 to about 1.5PHR (e.g., film samples 36 and 37).

Example 3: compatibility of the Membrane with 1-bromo-3-chloro-5, 5-dimethylhydantoin (BCDMH)

1-bromo-3-chloro-5, 5-dimethylhydantoin is also considered to be a more caustic oxidant. BCDMH is an excellent source of chlorine and bromine because it reacts slowly with water that releases hypochlorous and hypobromous acids. Water-soluble films comprising PVOH/monomethyl maleate or PVOH/2-acrylamide-2-methylpropanesulfonic Acid (AMPS) copolymers were prepared having the plasticizers described in tables 4 and 5 below. The thickness of the film was 2 mils (about 50 μm). Pouches were prepared by encapsulating 16mg of 1-bromo-3-chloro-5, 5-dimethylhydantoin in the film. The solubility of the water soluble film of the water soluble pouch was tested at t ═ 0 (no storage), 2 weeks, 4 weeks, and 6 weeks. The bags were stored at 23 ℃ and 35% RH. The dissolution time of each bag was determined at 21 ℃ according to MSTM 205. The films dissolved within 600 seconds after 6 weeks of storage are indicated as (+). The film that did not dissolve within 600 seconds after 6 weeks of storage was designated (-) in tables 4 and 5.

TABLE 4

Table 4 shows that when the total amount of plasticizer is less than 20PHR, films comprising a PVOH copolymer having an anionic monomer and having a first plasticizer comprising sorbitol and a second plasticizer comprising glycerin and trimethylolpropane are compatible with 1-bromo-3-chloro-5, 5-dimethylhydantoin.

Table 4 shows that films of the present disclosure comprising a PVOH copolymer comprising an anionic monomer having pendant carboxyl groups and having a first plasticizer comprising sorbitol and at least one trimethylolpropane, glycerol propylene oxide polymer (e.g., Voranol) are compatible with 1-bromo-3-chloro-5, 5-dimethylhydantoin when the total amount of plasticizer is in the range of 12PHR to 20PHR^TM230-660) or diacetin. Further, when the total amount of plasticizer is less than 12phr, the films of the present disclosure comprising a PVOH copolymer comprising an anionic monomer having a pendant carboxyl group, and having a first plasticizer comprising sorbitol and at least one 2-methyl-1, 3-propanediol, trimethylolpropane, glycerol propylene oxide polymer (e.g., Voranol) are compatible with 1-bromo-3-chloro-5, 5-dimethylhydantoin^TM230-660) and a second plasticizer of diacetin.

TABLE 5

Table 5 shows that films comprising a PVOH copolymer comprising an anionic monomer unit having a pendant carboxyl group, the film further comprising a first plasticizer comprising sorbitol, and a second plasticizer comprising glycerol and at least one of diglycerol or trimethylolpropane, are compatible with 1-bromo-3-chloro-5, 5-dimethylhydantoin (e.g., samples 43, 47, and 51).

Example 4: vertical form, fill and seal

A water-soluble film comprising a PVOH/monomethyl maleate copolymer was prepared having the plasticizers described in table 6 below. The thickness of the film was 2 mils (about 50 μm). The convertibility of the films was determined by VFFS as described above. Films that successfully formed a sealed package of about 5 inches by 9 inches and containing about 1.2 pounds (about 550 grams) of salt are indicated in table 6 as (+) above.

Table 6:

table 6 shows that films of the present disclosure comprising PVOH copolymers comprising anionic monomers having pendant carboxyl groups, and having a first plasticizer comprising sorbitol and a second plasticizer comprising glycerol and at least one trimethylolpropane or diglycerol, and having a total amount of plasticizer in the range of 12PHR to 20PHR can be converted into sealed pouches. Further, the films of the present disclosure comprising a PVOH copolymer comprising an anionic monomer having pendant carboxyl groups and having a first plasticizer comprising sorbitol and a second plasticizer comprising glycerol and at least one of trimethylolpropane and diglycerol, and having a total amount of plasticizers of less than 12phr, can be converted into sealed pouches. Table 6 also shows that a film comprising a PVOH copolymer having an anionic monomer with pendant carboxyl groups can be converted into a pouch, the film further comprising a total plasticizer amount greater than 20PHR, wherein at least 1/3 of the total plasticizer amount is sorbitol. In addition, as shown in tables 1 and 2, films successfully converted into pouches by VFFS were also compatible with trichloroisocyanurates. Thus, tables 1, 2, and 6 demonstrate that the films of the present disclosure are advantageously stable to caustic oxidizing chemicals while maintaining the ability to form pouches/bags.

The foregoing description is given for clearness of understanding only, and no unnecessary limitations should be understood therefrom, as modifications within the scope of the invention may be apparent to those having ordinary skill in the art.

All patents, publications, and references cited herein are hereby incorporated by reference in their entirety. In the event of a conflict between the present disclosure and the incorporated patents, publications, and references, the present disclosure shall control.

Claims

1. A sealed bag comprising a water-soluble film, the film comprising a mixture of a water-soluble polyvinyl alcohol copolymer (PVOH copolymer) and a plasticizer blend, the copolymer comprising an anionic monomer having pendant carboxyl groups, and the plasticizer blend comprising a first plasticizer and a second plasticizer, the first plasticizer comprising sorbitol, and the second plasticizer selected from the group consisting of: glycerin, trimethylolpropane, diglycerin, glycerol propylene oxide polymer, glycerol diacetate, 2-methyl-1, 3-propanediol, and combinations thereof, wherein the total amount of plasticizer in the film is in the range of 2PHR to 30PHR, and

(ii) when the total amount of plasticizer included in the film is at least 12PHR and less than 20PHR, then the plasticizer blend comprises sorbitol, glycerol, and at least one additional second plasticizer selected from diglycerol, trimethylolpropane, and combinations thereof; and

(iii) when the total amount of plasticizer included in the film is 20PHR or greater, then the plasticizer blend consists of sorbitol and the second plasticizer, wherein the second plasticizer is selected from the group consisting of: glycerol, trimethylolpropane, and two or more of glycerol, trimethylolpropane, diglycerol, glycerol propylene oxide polymer, glycerol diacetate, and 2-methyl-1, 3-propanediol, and the sorbitol comprises at least 1/3 by weight of the total amount of plasticizer;

wherein the sealed bag encapsulates an oxidizing composition.

2. The sealed bag of claim 1, wherein when glycerin is included in the film, glycerin is included in an amount of at least 2.0 wt.%, based on the total weight of the film.

3. The sealed bag of claim 1 or claim 2, wherein the total amount of plasticizer in the film is at least 5PHR, based on the total resin in the film.

4. The sealed bag of claim 1 or claim 2, wherein the total amount of plasticizer is less than 12PHR, based on the total resin in the film.

5. The sealed bag of claim 1 or claim 2, wherein the total amount of plasticizer in the film is in the range of 15 to 20PHR, based on the total resin in the film.

6. The sealed bag of claim 1 or claim 2, wherein the total amount of plasticizer in the film is in the range of 21PHR to 27PHR, based on the total resin in the film.

7. The sealed pouch of claim 1 or claim 2, wherein the anionic monomeric unit is selected from the group consisting of: vinyl acetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, alkali metal salts of the foregoing, esters of the foregoing, and combinations of the foregoing.

8. The sealed bag of claim 7, wherein the monoalkyl ester of maleic acid is monomethyl maleate, the dialkyl ester of maleic acid is dimethyl maleate, the monoalkyl ester of fumaric acid is monomethyl fumarate, and the dialkyl ester of fumaric acid is dimethyl fumarate.

9. The sealed bag of claim 7, wherein the anionic monomer units comprise one or more of maleic acid, monoalkyl maleates, dialkyl maleates, maleic anhydride, alkali metal salts of the foregoing, esters of the foregoing, and combinations thereof.

10. The sealed pouch of claim 9, wherein the anionic monomeric unit is selected from the group consisting of: maleic acid, monomethyl maleate, dimethyl maleate, maleic anhydride, alkali metal salts of the foregoing, esters of the foregoing, and combinations thereof.

11. The sealed bag of claim 1 or claim 2, wherein the PVOH copolymer comprises a degree of hydrolysis in a range of 87 to 98.

12. The sealed bag of claim 11, wherein the PVOH copolymer has a degree of hydrolysis in a range of 94 to 98.

13. The sealed bag of claim 12, wherein the PVOH copolymer has a degree of hydrolysis of 96.

14. The sealed bag of claim 1 or claim 2, further comprising an antioxidant.

15. The sealed bag of claim 14, wherein the antioxidant is selected from the group consisting of: sodium metabisulfite, propyl gallate, citric acid, and combinations thereof.

16. The sealed bag of claim 1 or claim 2, wherein after storage in contact with a caustic chemical oxidizer for 6 weeks at 23 ℃ and 35% Relative Humidity (RH), a film having the same composition and 2 mil (0.05 mm) thickness dissolves in water in 600 seconds or less at a temperature of 20 ℃ (68 ° f) according to MonoSol test method MSTM-205.

17. The sealed bag of claim 1 or claim 2, further comprising a filler, a surfactant, an anti-blocking agent, or a combination of the foregoing.

18. The sealed bag of claim 1, wherein the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 7 to 8PHR, and the plasticizer blend consists of glycerin, sorbitol, and diglycerin.

19. The sealed bag of claim 1, wherein the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 7 to 8PHR, and the plasticizer blend consists of glycerol, sorbitol, and trimethylolpropane.

20. The sealed bag of claim 1, wherein the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 24 to 25PHR, and the plasticizer blend consists of a 1:1 wt% mixture of glycerin and sorbitol.

21. The sealed bag of claim 1, wherein the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 24 to 25PHR, and the plasticizer blend consists of a 1:1wt mixture of trimethylolpropane and sorbitol.

22. The sealed bag of claim 1, wherein the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 24 to 25PHR, and the plasticizer blend consists of a 1:1:1 wt% mixture of trimethylolpropane, glycerol, and sorbitol.

23. The sealed bag of claim 1, wherein the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 16.5 to 17.5PHR, and the plasticizer blend consists of glycerin, sorbitol, and diglycerin.

24. The sealed bag of claim 1, wherein the anionic monomer comprises monomethyl maleate, the total plasticizer present in the film is in the range of 16.5 to 17.5PHR, and the plasticizer blend consists of glycerol, sorbitol, and trimethylolpropane.

25. The sealed bag of claim 1 or claim 2, wherein the bag is a vertical form, fill, and seal bag.

26. The sealed bag of claim 1 or claim 2, wherein the oxidizing composition is a chlorinated or brominated composition.

27. The sealed bag of claim 1 or claim 2, wherein the oxidizing composition is selected from the group consisting of: sodium hypochlorite, calcium hypochlorite and lithium hypochlorite, dichloroisocyanuric acid, trichloroisocyanuric acid, Trichloroisocyanurate (TC), salts and hydrates of the foregoing, 1, 3-dibromo-5, 5-dimethylhydantoin (DBDMH), 2-dibromo-3-nitrilopropionamide (DBNPA), dibromocyanoacetic acid amide, 1-bromo-3-chloro-5, 5-dimethylhydantoin (BCDMH), 2-bromo-2-nitro-1, 3-propanediol, and combinations thereof.

28. The sealed bag of claim 1 or claim 2, wherein the oxidizing composition is selected from the group consisting of: trichloroisocyanurates, 1-bromo-3-chloro-5, 5-dimethylhydantoin, and combinations thereof.

29. The sealed bag of claim 27, wherein the bag has an internal volume of at least 25 ml.

30. The sealed bag of claim 27, wherein the bag has a length of at least 12.5cm (5 inches).

31. A water-soluble film for packaging an oxidizing composition in contact with the film, the film comprising a mixture of a water-soluble polyvinyl alcohol copolymer and a plasticizer blend, the copolymer including an anionic monomer having pendant carboxyl groups, and the plasticizer blend comprising a first plasticizer and a second plasticizer, the first plasticizer comprising sorbitol, and the second plasticizer selected from the group consisting of: glycerin, trimethylolpropane, diglycerin, glycerol propylene oxide polymer, glycerol diacetate, 2-methyl-1, 3-propanediol, and combinations thereof, wherein the total amount of plasticizer in the film is in the range of 2PHR to 30PHR, and

(iii) when the total amount of plasticizer included in the film is 20PHR or greater, then the plasticizer blend consists of sorbitol and the second plasticizer, wherein the second plasticizer is selected from the group consisting of: glycerol, trimethylolpropane, and two or more of glycerol, trimethylolpropane, diglycerol, glycerol propylene oxide polymer, glycerol diacetate, and 2-methyl-1, 3-propanediol, and the sorbitol comprises at least 1/3 by weight of the total amount of plasticizer.

32. The water-soluble film of claim 31, wherein the film takes the form of a sealed pouch containing the oxidizing composition.

33. The sealed bag of claim 3, wherein the total amount of plasticizer in the film is at least 6.5PHR, based on the total resin in the film.

34. The sealed bag of claim 4, wherein the total amount of plasticizer is less than 10PHR, based on the total resin in the film.

35. The sealed bag of claim 4, wherein the total amount of plasticizer is less than 8PHR, based on the total resin in the film.

36. The sealed bag of claim 4, wherein the total amount of plasticizer is less than 7.5PHR, based on the total resin in the film.

37. The sealed bag of claim 5, wherein the total amount of plasticizer in the film is in the range of 16 to 18PHR, based on the total resin in the film.

38. The sealed bag of claim 6, wherein the total amount of plasticizer in the film is in the range of 23 to 25PHR, based on the total resin in the film.

39. The sealed bag of claim 11, wherein the PVOH copolymer comprises a degree of hydrolysis in a range of 89 to 97.

40. The sealed bag of claim 11, wherein the PVOH copolymer comprises a degree of hydrolysis in a range of 90 to 96.

41. The sealed bag of claim 29, wherein the bag has an internal volume of at least 100 ml.

42. The sealed bag of claim 29, wherein the bag has an internal volume of at least 150 ml.

43. The sealed bag of claim 29, wherein the bag has an internal volume of at least 200 ml.

44. The sealed bag of claim 29, wherein the bag has an internal volume of at least 250 ml.

45. The sealed bag of claim 29, wherein the bag has an internal volume of at least 300 ml.

46. The sealed bag of claim 30, wherein the bag has a length of at least 18cm (7 inches).

47. The sealed bag of claim 30, wherein the bag has a length of at least 23cm (9 inches).